Stereodiscrimination in Phosphanylthiolato Nickel(II) Complexes

Josep Duran, Alfonso Polo, Julio Real, Jordi Benet-Buchholz, Albert Poater, Miquel Solà

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11 Citations (Scopus)

Abstract

The presence of a stereogenic carbon centre (R or S) in the racemic ligand 1-(diphenylphosphanyl)propane-2-thiol induces a conformational preference (λ of δ) in the five-membered chelate ring of its 2:1 and 2:2 coordination compounds with NiII: the mononuclear trans-[Ni{SCH(CH3)CH2PPh2-P,S}2] (1) and the binuclear trans-[Ni{μ-SCH(CH3)CH2PPh 2-P,S}(Cl)]2 (2). Both complexes exist as mixtures of two diastereomers: racemic-trans (Rλ, Rλ, & and Sδ, Sδ) and meso-trans (R λ, Sδ), in an equilibrium displaced towards the more stable isomer, the meso-trans for 1 (calculated ΔE = < -0.1 kcal·mol-1) and the racemic-trans for 2 (calculated ΔE = -5.1 kcal·mol-1). This phenomenon is especially evident for complex 2, in which an efficient chiral recognition between the two enantiomeric forms of the racemic ligand was observed. © Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.
Original languageEnglish
Pages (from-to)4147-4151
JournalEuropean Journal of Inorganic Chemistry
Issue number23
DOIs
Publication statusPublished - 5 Dec 2003

Keywords

  • Chiral resolution
  • Conformation analysis
  • Density functional calculations
  • Nickel
  • P,S ligands

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